CN113862015A - Method for promoting quality of pyrolysis oil to be improved by seawater electrochemical pretreatment of biomass and application - Google Patents
Method for promoting quality of pyrolysis oil to be improved by seawater electrochemical pretreatment of biomass and application Download PDFInfo
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- CN113862015A CN113862015A CN202111382561.9A CN202111382561A CN113862015A CN 113862015 A CN113862015 A CN 113862015A CN 202111382561 A CN202111382561 A CN 202111382561A CN 113862015 A CN113862015 A CN 113862015A
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- biomass
- pyrolysis oil
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
- C10G1/042—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction by the use of hydrogen-donor solvents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/042—Electrodes formed of a single material
- C25B11/043—Carbon, e.g. diamond or graphene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a method for promoting the quality of pyrolysis oil to be improved by seawater electrochemical pretreatment of biomass and application thereof. The method comprises the following steps: (1) crushing and screening a biomass raw material, adding the crushed and screened biomass raw material into a salt solution, uniformly mixing, then carrying out an electrolytic reaction under the conditions of stirring and applied voltage, wherein the voltage is 5-15V and the time is 2-8 hours, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain a pretreated biomass; wherein the salt solution is a NaCl solution or seawater with the concentration of 2-6.5% by mass; (2) and (3) pyrolyzing the pretreated biomass in a protective gas atmosphere at 400-600 ℃ for 30-90 min, and collecting pyrolysis oil by using an organic solvent. After pretreatment by the method, the cellulose content in the biomass can be increased, the lignin content can be reduced, the content of levoglucosan and furfural in the obtained pyrolysis oil is obviously increased, and the quality of the pyrolysis oil is improved.
Description
Technical Field
The invention relates to the field of biomass energy, in particular to a method for promoting the quality of pyrolysis oil to be improved by electrochemically pretreating biomass with seawater and application thereof.
Background
Lignocellulose, as a renewable, green and sustainable resource, is considered as one of the alternative sources of fossil energy, which can produce high-value chemicals and pharmaceutical additives. Among them, fast pyrolysis is considered to be a process with low economic investment and high liquid yield, and is the most efficient way to convert lignocellulose into chemical products. However, the bio-oil produced by fast pyrolysis is an extremely complex mixture consisting of water and hundreds of organic oxygenates, such as furans, pyrans, hydrogen-free sugars and phenols. Among them, produced Levoglucosan (LG) and furfural are promising bulk chemical agents useful as surfactants, plastics, drugs and resins. But the very low concentrations of LG and furfural in bio-oils lead to problems in extraction and subsequent purification. In order to increase the content of LG and furfural and reduce the synthesis cost of middle-downstream added-value chemicals, the composition and structure of biomass need to be adjusted through pretreatment.
Generally, pretreatment methods can be classified into four types of physical, chemical, physicochemical, and biological pretreatment. However, typical pretreatment conditions such as hydrothermal, acid and alkali pretreatment are severe, and waste liquid treatment is difficult and environmentally-friendly. Furthermore, ionic liquid and eutectic solvent pretreatment is considered a green and environmentally friendly means, but its application is limited by high cost and immature recovery technology. Thus, an efficient, economical, green approach to pre-processing remains a formidable challenge. For decades, electrochemistry has been recognized as an effective way to degrade contaminants in water, to organically selectively convert, and to make corrosion resistant materials. The unique ability of electrochemistry to produce redox species or reactive intermediates under mild conditions provides a new possibility for the isolation of lignocellulose from biomass. During the electrochemical process, some components in the biomass are degraded by reactive intermediates, causing changes in composition and structure. Furthermore, as a means of lignocellulose separation, it is attractive to additionally obtain a commercially valuable by-product (hydrogen) in an electrochemical pretreatment. Electrochemical pretreatment of biomass under mild conditions is therefore a promising approach.
In previous studies on electrochemical pretreatment, electrolytes have a great influence on the electrochemical pretreatment of biomass. Maazuza et al pretreat biomass with an ionic liquid-promoted organic solvent as the electrolyte. For aqueous electrolytes, different solutes determine the role of the external voltage in the electrochemical pretreatment. In one aspect, the external voltage restores the oxidative properties of the solute resulting in continuous removal of lignin. On the other hand, according to the oxidation pathway, the external voltage promotes the conversion of the lignin dissolved by the electrolyte. Therefore, it remains a challenge to find an inexpensive and economical electrolyte.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a method for promoting the quality of pyrolysis oil by electrochemically pretreating biomass by using seawater or a simulant thereof as electrolyte.
The invention also aims to provide application of the method for promoting the quality of pyrolysis oil by electrochemically pretreating biomass with seawater.
The purpose of the invention is realized by the following technical scheme:
a method for promoting the quality of pyrolysis oil by seawater electrochemical pretreatment of biomass comprises the following steps:
(1) electrochemical pretreatment: crushing and sieving a biomass raw material, adding the crushed and sieved biomass raw material into a salt solution, uniformly mixing, then carrying out an electrolytic reaction under the conditions of stirring and applied voltage, wherein the voltage is 5-15V and the time is 2-8 hours, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain a pretreated biomass (the content of cellulose in the biomass can be increased and the content of lignin in the biomass can be reduced); wherein the salt solution is a NaCl solution or seawater with the concentration of 2-6.5% by mass;
(2) pyrolysis: and (2) pyrolyzing the pretreated biomass obtained in the step (1) in a protective gas atmosphere at 400-600 ℃ for 30-90 min, and collecting pyrolysis oil by using an organic solvent.
The biomass raw material in the step (1) is a conventional biomass raw material, such as a waste agriculture and forestry biomass raw material; preferably a biomass feedstock having a relatively high content of cellulose and hemicellulose; more preferably corn stover.
The pulverization in the step (1) is preferably performed by a pulverizer.
Sieving in the step (1) is to sieve the mixture by a sieve of 40-200 meshes; preferably, the sieve is 80-100 meshes.
The concentration of the NaCl solution in the step (1) is preferably 2-5% by mass; further preferably 2-3.5% by mass; more preferably 3.5% by mass (the world average seawater salt concentration is 35 g/Kg).
The solid-liquid ratio of the biomass raw material to the salt solution in the step (1) is 1: 100 to 150 parts; g/ml; preferably 1: 100, respectively; g/ml, the proportion is required to ensure that the solid biomass raw material can be fully contacted with the solution.
The stirring conditions in the step (1) are as follows: stirring at 400-800 r/min for 10-40 min, wherein the stirring aims at enabling the raw materials to fully react with the intermediate generated by electrolysis in the reaction process; preferably 600r/min for 20 min.
The electrodes used in the electrochemical pretreatment in the step (1) are graphite electrodes (preferably graphite electrodes with the size of 6 x 95 mm), the distance between the two electrodes (positive and negative electrodes) is 6cm, the power supply used is an adjustable direct current power supply, and the electrolytic cell is a diaphragm-free electrolytic cell.
The electrolysis reaction in the step (1) can be carried out in an 800ml glass electrolytic cell (taking 500ml of salt solution as an example) to prevent the electrolyte from damaging the electrolytic cell; wherein the electrolytic cell is a diaphragm-free electrolytic cell.
The voltage of the electrolytic reaction in the step (1) is preferably 10-15V; more preferably 15V.
The temperature of the electrolytic reaction in the step (1) is preferably room temperature.
The time of the electrolytic reaction in the step (1) is preferably 4-8 hours; more preferably 8 hours.
The washing in the step (1) is carried out by sequentially adopting water, acetone and water until the filtrate is colorless and transparent.
The drying temperature in the step (1) is 50-105 ℃; preferably 105 deg.c.
The drying time in the step (1) is 5-24 hours; preferably 8 hours.
The pyrolysis in the step (2) is pyrolysis in a tubular furnace; the pyrolysis is preferably carried out in a quartz tube fixed bed reactor with the length of 500mm and the diameter of 35mm, the using amount of pretreated biomass in the reactor is 0.5-2 g (preferably 0.5g), and quartz wool is placed at the bottom of the biomass, so that pyrolytic biochar is separated from pyrolytic bio-oil.
The protective gas in the step (2) is inert gas; preferably, the nitrogen is used, the gas flow is preferably 400-600 ml/min (preferably 550ml/min), and the high flow rate prevents the repolymerization reaction of the pyrolysis oil product in the pyrolysis process.
The temperature of the pyrolysis described in step (2) is preferably 500 ℃.
The collection in the step (2) is carried out in a condensation device, and the condensed liquid in the condensation device is preferably industrial ethanol.
The condensation temperature during the collection in the step (2) is-10 to-20 ℃; preferably-18 ℃.
The pyrolysis time in step (2) is preferably 30 min.
The organic solvent in step (2) is preferably acetone.
The method for promoting the quality of the pyrolysis oil to be improved by electrochemically pretreating biomass with seawater is applied to preparation of the pyrolysis oil, levoglucosan and/or furfural.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention provides a pretreatment method of waste biomass (such as corn straws), which can adjust the components and the structure of the biomass, improve the cellulose content in the biomass, reduce the lignin content in the biomass, change the structure of the biomass to generate a new pore channel structure in the biomass, and realize waste utilization due to low price of waste biomass raw materials.
(2) The invention provides a biomass electrochemical pretreatment (electricity-assisted seawater pretreatment) method, which can take seawater or a NaCl aqueous solution of a simulant thereof as electrolyte without other additional chemical reagents.
(3) The invention provides a method for improving the quality of biological oil, which is characterized in that after biomass is pretreated, pyrolysis is carried out, the content of levoglucosan in the biological oil is increased from 0% to 31.24% at most (voltage is 15V, time is 8h), and the content of furfural is increased from 4.03% to 14.15% at most (voltage is 15V, time is 4 h).
Drawings
FIG. 1 is a graph of solids yield and lignocellulosic composition under different electrochemical pretreatment conditions; wherein A is the solid yield and the lignocellulose composition condition under different voltages; b is the solid yield and the lignocellulose composition condition under different pretreatment time; c is the solids yield and lignocellulosic composition at different salt concentrations.
FIG. 2 is a graph of pyrolysis bio-oil distribution under different electrochemical pretreatment conditions; wherein a is the distribution condition of the pyrolysis bio-oil under different voltages; b is the distribution condition of the pyrolysis bio-oil under different pretreatment time; c is the distribution of the pyrolysis bio-oil under different salt concentrations.
FIG. 3 is a graph of the relative content of typical compounds in pyrolysis oil under different electrochemical pretreatment conditions; wherein a is the relative content of typical compounds at different voltages; b is the relative content of typical compounds at different pretreatment times; c is the relative content of typical compounds at different salt concentrations.
FIG. 4 is a graph showing the results of XPS analysis of pretreated biomass under different electrochemical pretreatment conditions.
FIG. 5 is a graph showing the results of FT-IR analysis of pretreated biomass under different electrochemical pretreatment conditions.
FIG. 6 is an SEM image of pretreated biomass under different electrochemical pretreatment conditions; wherein a is as received; b is 5V-4 h; c is 10V-4 h; d is 15V-4 h; e is seawater; f is 6.5 wt%.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The test methods in the following examples, in which specific experimental conditions are not specified, are generally performed according to conventional experimental conditions or according to the experimental conditions recommended by the manufacturer. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
NaCl (AR 99.5%) involved in the examples of the present invention was purchased from Shanghai Michelin Biochemical technology, Inc.
The seawater related in the embodiment of the invention is taken from coastal coral reef areas of Weihai in Shandong province.
The corn straws related in the embodiment of the invention are purchased from Henan province and then pretreated: crushing the received corn straws by using a crusher, screening 80-100 meshes of corn straws, drying the corn straws for 24 hours at 105 ℃, and finally collecting the corn straws in a sealed bag for subsequent pretreatment and pyrolysis experiments.
In the embodiment of the application, the biomass pyrolysis oil reaction product is tested by using a gas mass spectrometry-mass spectrometry (GC-MS), and is calculated according to the test result by using the following formula:
in the formula, R1、R2……RnIs the GC-MS percentage (%) of each substance in the liquid phase product.
The GC-MS measurement conditions were as follows: the specific composition of the fast pyrolysis bio-oil is determined by gas chromatography-mass spectrometry using Agilent 7890b-5977A equipped with Ptx-Wax column (30.00 m.times.0.25 mm.times.0.25 μm). The evaporator temperature was set at 280 ℃. The column temperature was controlled by a temperature program, specifically an initial temperature of 40 ℃ and held for 5 min. Subsequently, it was increased to 150 ℃ at a rate of 10 ℃/min. Then increased to 200 ℃ at a rate of 5 ℃/min and held for 5 min. Finally, it was raised to 240 ℃ at a rate of 10 ℃/min and held at this temperature for 8 min.
The invention adopts a two-step sulfuric acid (mass fraction of 72 percent and 4 percent) hydrolysis method (adopting a National Renewable Energy Laboratory (NREL) method) to determine the content of lignin, cellulose and hemicellulose in corn straw original sample and electrochemical pretreatment sample.
The solids yield was calculated as follows:
solid yield (%) ═ remaining solids (g)/raw biomass (g) × 100%;
water soluble phase (%) -% 100% solid yield.
In order to eliminate the influence of impurities in the seawater, the invention adopts 3.5 wt% NaCl solution (the world average seawater salt concentration is 35g/Kg) as seawater simulator for electrochemical pretreatment.
EXAMPLE 1 different Voltage electrochemical pretreatment
(1) Weighing 17.5g NaCl in an electrolytic cell (800ml glass electrolytic cell to prevent the electrolyte from damaging the electrolytic cell), adding 500ml deionized water, placing on an electronic stirrer, and stirring at 600r/min until the solution has no obvious NaCl crystal (3.5 wt% NaCl solution). Crushing the received corn straws by using a crusher, sieving and drying, selecting 5g of biomass of 80-100 meshes, adding the biomass into a diaphragm-free electrolytic cell, and stirring at the rotating speed of 600r/min for 20min until the biomass is uniformly mixed. Two 6 x 95mm graphite electrodes were inserted into a diaphragm-free electrolytic cell, the distance between the two electrodes (i.e. the gap between the two electrodes) being set at 6 cm. The external voltage is controlled to be 5, 10 and 15V by an adjustable direct current adjusting power supply (MS3010DS), the power is supplied for 4h, and stirring is continuously carried out at the rotating speed of 600r/min in the process. And after the reaction is finished, performing suction filtration on the mixture obtained after the pretreatment reaction, cleaning and performing suction filtration for 1 time by using clear water, cleaning and performing suction filtration by using acetone (so as to wash away degradation products in the biomass pretreatment process), and finally washing by using clear water until the filtrate is colorless and transparent. The solid was placed in an oven at 105 ℃ for 8 h. Samples subjected to electrochemical pretreatment at different voltages are named as 5V-4h, 10V-4h and 15V-4h respectively; meanwhile, untreated corn stover was designated as stock (CS) as a control.
(2) The pyrolysis reaction was carried out in a quartz tube fixed-bed reactor having a length of 500mm and a diameter of 35 mm. A0.5 g sample was placed in the middle of the fixed bed and quartz wool was placed at the bottom. To prevent the repolymerization of the gaseous product, high purity nitrogen at a flow rate of 550mL/min was used as a shielding gas. When the furnace temperature was heated to 500 ℃, the quartz tube was quickly inserted into the furnace and the bio-oil produced by pyrolysis was liquefied with a-18 ℃ condensing unit (the condensate was industrial ethanol). The pyrolysis reaction lasted for 0.5 hours. After the reaction was completed, the quartz tube was taken out and cooled to room temperature. The bio-oil was acetone and collected in a serum bottle.
EXAMPLE 2 electrochemical pretreatment at different times
(1) 17.5g NaCl was weighed into an electrolytic cell (800ml glass diaphragm-free electrolytic cell), 500ml deionized water was added, and the solution was stirred on an electronic stirrer at 600r/min until no significant NaCl crystals (3.5 wt% NaCl solution) were present in the solution. Crushing the received corn straws by using a crusher, sieving and drying, selecting 5g of biomass of 80-100 meshes, adding the biomass into a diaphragm-free electrolytic cell, and stirring at the rotating speed of 600r/min for 20min until the biomass is uniformly mixed. Two 6 x 95mm graphite electrodes were inserted into a diaphragm-free electrolytic cell, the distance between the two electrodes being set at 6 cm. The external voltage is controlled to be 15V by an adjustable direct current adjusting power supply (MS3010DS), the power is supplied for 2, 4, 6 and 8 hours, and stirring is continuously carried out at the rotating speed of 600r/min in the process. And after the reaction is finished, performing suction filtration on the mixture obtained after the pretreatment reaction, cleaning and performing suction filtration for 1 time by using clear water, cleaning and performing suction filtration by using acetone (so as to wash away degradation products in the biomass pretreatment process), and finally washing by using clear water until the filtrate is colorless and transparent. The solid was placed in an oven at 105 ℃ for 8 h. Samples subjected to electrochemical pretreatment at different time are named as 15V-2h, 15V-4h, 15V-6h and 15V-8h respectively.
(2) The pyrolysis reaction was carried out in a quartz tube fixed-bed reactor having a length of 500mm and a diameter of 35 mm. A0.5 g sample was placed in the middle of the fixed bed and quartz wool was placed at the bottom. To prevent the repolymerization of the gaseous product, high purity nitrogen at a flow rate of 550mL/min was used as a shielding gas. When the furnace temperature was heated to 500 ℃, the quartz tube was quickly inserted into the furnace and the bio-oil produced by pyrolysis was liquefied with a-18 ℃ condensing unit (the condensate was industrial ethanol). The pyrolysis reaction lasted for 0.5 hours. After the reaction was completed, the quartz tube was taken out and cooled to room temperature. The bio-oil was acetone and collected in a serum bottle.
EXAMPLE 3 different concentrations of electrochemical pretreatment
(1) Weighing 10 g, 17.5g, 25 g and 32.5g of NaCl in an electrolytic bath (800ml of glass diaphragm-free electrolytic bath), adding 500ml of deionized water, and placing on an electronic stirrer to stir at 600r/min until the solution has no obvious NaCl crystals (2%, 3.5%, 5% and 6.5% NaCl solution). Crushing the received corn straws by using a crusher, sieving and drying, selecting 5g of biomass of 80-100 meshes, adding the biomass into a diaphragm-free electrolytic cell, and stirring at the rotating speed of 600r/min for 20min until the biomass is uniformly mixed. Two 6 x 95mm graphite electrodes were inserted into a diaphragm-free electrolytic cell, the distance between the two electrodes being set at 6 cm. The external voltage is controlled to be 15V by an adjustable direct current adjusting power supply (MS3010DS), the power is supplied for 4h, and stirring is continuously carried out at the rotating speed of 600r/min in the process. And after the reaction is finished, performing suction filtration on the mixture obtained after the pretreatment reaction, cleaning and performing suction filtration for 1 time by using clear water, cleaning and performing suction filtration by using acetone (so as to wash away degradation products in the biomass pretreatment process), and finally washing by using clear water until the filtrate is colorless and transparent. The solid was placed in an oven at 105 ℃ for 8 h. Samples after electrochemical pretreatment with different concentrations were named 2%, 3.5%, 5%, 6.5%, respectively.
(2) The pyrolysis reaction was carried out in a quartz tube fixed-bed reactor having a length of 500mm and a diameter of 35 mm. A0.5 g sample was placed in the middle of the fixed bed and quartz wool was placed at the bottom. To prevent the repolymerization of the gaseous product, high purity nitrogen at a flow rate of 550mL/min was used as a shielding gas. When the furnace temperature was heated to 500 ℃, the quartz tube was quickly inserted into the furnace and the bio-oil produced by pyrolysis was liquefied with a-18 ℃ condensing unit (the condensate was industrial ethanol). The pyrolysis reaction lasted for 0.5 hours. After the reaction was completed, the quartz tube was taken out and cooled to room temperature. The bio-oil was acetone and collected in a serum bottle.
EXAMPLE 4 real seawater electrochemical pretreatment
(1) 500ml of seawater is taken and placed in an electrolytic cell (800ml of glass diaphragm-free electrolytic cell), then the received corn straws are crushed by a crusher, sieved and dried, 5g of biomass of 80-100 meshes is selected and added into the diaphragm-free electrolytic cell, and the mixture is stirred at the rotating speed of 600r/min for 20min until being uniformly mixed. Two 6 x 95mm graphite electrodes were inserted into a diaphragm-free electrolytic cell, the distance between the two electrodes being set at 6 cm. The external voltage is controlled to be 15V by an adjustable direct current adjusting power supply (MS3010DS), the power is supplied for 4h, and stirring is continuously carried out at the rotating speed of 600r/min in the process. And after the reaction is finished, performing suction filtration on the mixture obtained after the pretreatment reaction, cleaning and performing suction filtration for 1 time by using clear water, cleaning and performing suction filtration by using acetone (so as to wash away degradation products in the biomass pretreatment process), and finally washing by using clear water until the filtrate is colorless and transparent. The solid was placed in an oven at 105 ℃ for 8 h. The sample electrochemically pretreated with seawater was named Seawater (SW).
(2) The pyrolysis reaction was carried out in a quartz tube fixed-bed reactor having a length of 500mm and a diameter of 35 mm. A0.5 g sample was placed in the middle of the fixed bed and quartz wool was placed at the bottom. To prevent the repolymerization of the gaseous product, high purity nitrogen at a flow rate of 550mL/min was used as a shielding gas. When the furnace temperature was heated to 500 ℃, the quartz tube was quickly inserted into the furnace and the bio-oil produced by pyrolysis was liquefied with a-18 ℃ condensing unit (the condensate was industrial ethanol). The pyrolysis reaction lasted for 0.5 hours. After the reaction was completed, the quartz tube was taken out and cooled to room temperature. The bio-oil was acetone and collected in a serum bottle.
Effects of the embodiment
The contents of lignin, cellulose and hemicellulose, as well as the solid yield and the water-soluble phase in examples 1 to 4 were determined as described above; the biomass pyrolysis oil reaction products collected in examples 1 to 4 were tested by gas mass spectrometry-mass spectrometry, and the results are shown in fig. 1 to 6 and table 1.
FIG. 1 shows solids yield and lignocellulosic composition under various pretreatment conditions, and the content of each component in corn stover was varied depending on the pretreatment conditions.
In fig. 1A, the solid yield dropped from 80.0% to 66.0% as the voltage increased from 5V to 15V. Figure 1A also shows that 95% of the cellulose in the biomass remained after pretreatment with different voltages having little effect on the cellulose content. It is well known that lignin is cross-linked with cellulose and hemicellulose by covalent hydrogen bonds, forming a complex three-dimensional network structure. Thus, during electrochemical pretreatment, some of the short chain cellulose or oligosaccharides in the biomass are dissolved in the water as the lignin degrades. As shown in table 1, as the voltage was increased, the relative content of cellulose increased from 31.78% to 46.71%, while the relative content of lignin decreased from 26.60% to 11.89%. These results indicate that electrochemical pretreatment of seawater can effectively remove lignin.
TABLE 1 corn stover and sample composition after pretreatment
| Chemical composition (%) | As received | 5V-4h | 10-4h | 15V- |
15V- |
15V- |
15V- |
2％ | 5％ | 6.50％ | Seawater, its production and use |
| Lignin | 26.60 | 23.44 | 18.85 | 11.89 | 17.52 | 10.81 | 8.90 | 18.35 | 7.16 | 5.49 | 14.35 |
| Cellulose, process for producing the same, and process for producing the same | 31.78 | 38.12 | 39.42 | 46.71 | 42.51 | 46.37 | 54.73 | 41.81 | 53.35 | 67.89 | 40.61 |
| Hemicellulose | 17.69 | 20.49 | 20.63 | 22.50 | 21.61 | 21.64 | 18.46 | 20.29 | 20.27 | 8.13 | 19.99 |
| |
0 | 29.49 | 45.29 | 70.50 | 49.67 | 75.46 | 83.46 | 49.64 | 86.43 | 92.86 | 63.53 |
The electrochemical pretreatment time also has an important influence on the solid yield. In fig. 1B, the solids yield of biomass decreased with increasing pretreatment time. Particularly, when the electrochemical time is increased by 2-8 h, the relative content of lignin is reduced from 17.52% to 8.90%, which is related to the attack of active Cl and OH on lignin. Due to the removal of lignin after pretreatment, the relative content of hemicellulose increased from 21.61% to 22.50% and reached a maximum at 4 hours.
Furthermore, the salt concentration also has an important influence on the electrochemical pretreatment, and from FIG. 1C, a similar phenomenon can be seen, where the hemicellulose content decreases to 8.13% when the NaCl concentration increases to 6.5%. This can be explained by the fact that during the electrochemical pretreatment, the higher the electrolyte concentration, the higher the current, the more heat energy is generated promoting the hydrolysis of hemicellulose. Previous studies have shown that ClO2 -The influence on hemicellulose is slight, and the fact that the hemicellulose is ClO can be inferredx -Deconstruction, ClOx -Has stronger oxidation performance and generates more ClO along with the increase of NaCl concentrationx -. At the same time, lignin is destroyed and hemicellulose and cellulose are apparentAnd is exposed. ClO-x reacts with them in solution, converting them into small molecules that are soluble in water, which is detrimental to cellulose enrichment. Therefore, the NaCl concentration of about 3.5 percent is beneficial to removing lignin and simultaneously beneficial to enriching cellulose and hemicellulose.
FIG. 2 shows the distribution of pyrolysis bio-oil under different pretreatment conditions.
As can be seen from fig. 2a, the relative amount of carbohydrate in the treated sample increases significantly with increasing applied voltage. The increase in sugar content from 2.07% to 10.46%, 30.69% and 36.82% at 5V, 10V and 15V, respectively, may be attributed primarily to the increase in the relative content of cellulose in the treated sample due to lignin decomposition under voltage treatment, and the formation of a porous structure that favors the escape of sugar volatiles. In addition, the removal or inactivation of alkaline earth metals inhibits the ring-opening reaction of carbohydrates during pyrolysis, and therefore, the removal of alkaline earth metals from the carbohydrate content of the bio-oil is also considered to be a critical factor. The ketone content is 14.68-18.14%, 20.90% and 23.64%. Aromatic hydrocarbons in the bio-oil are mainly derived from the pyrolysis of lignin, and the relative content of aromatic substances in the pyrolyzed bio-oil is 42.53%, 38.13%, 15.47% and 7.87%, which respectively correspond to CS, 5V-4h, 10V-4h and 15V-4h samples. The aroma content decreases significantly with increasing pretreatment voltage. The results show that: as the electrochemical pretreatment voltage is increased, the relative content of lignin is reduced from 26.60% to 11.89%, so that the aromatic substances are reduced; and the ash content decreases with increasing voltage, leaching of the ash (ash dissolved in water) leads to a reduction of volatile substances during the pyrolysis of the lignin due to the catalytic action of the ash. In addition, the content of furan is reduced along with the increase of the pretreatment voltage due to the reduction of aromatic free radicals of an intermediate product generated by benzofuran.
As a result, it was found that during the electrochemical pretreatment, the decomposition of lignin causes the aromatic substances to decrease with increasing pretreatment time. However, as the pretreatment time increased, the relative content of aromatic material remained around 8% due to the free-radical rearrangement reaction caused by the cellulose. The sugar and ketone content increased with increasing pretreatment time, which is consistent with the change in cellulose content (table 1).
In addition, fig. 2c shows the distribution of the pyrolyzed bio-oil in the electrochemically pretreated samples at different NaCl concentrations. The sugar content slightly fluctuates between 33.18% and 36.83%. Especially, when the corn stalks are subjected to real seawater electrochemical pretreatment, the sugar content reaches 35.21 percent. High concentrations of NaCl pretreatment lead to the formation of oxidized cellulose, which may be detrimental to the subsequent pyrolysis to produce sugars.
FIG. 3 shows the relative amounts of typical compounds under different pretreatment conditions; FIGS. 4 and 5 show the results of X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT IR) analysis of biomass after various pretreatments; FIG. 6 shows SEM images of pretreated biomass under different electrochemical pretreatment conditions.
The effect of electrochemical pretreatment on typical compounds in bio-oil is compared in fig. 3. During pyrolysis of biomass, the predominant sugar produced by cleavage of the glycosidic bond of cellulose is Levoglucosan (LG), and the formation of LG and 5-hydroxymethylfurfural is a competing reaction. Figure 3a shows that LG and 5-hydroxymethylfurfural content rose from 0% to 23.22% and 3.62%, respectively.
This is affected in several ways: 1) ash is washed away during the electrochemical production process and ash is believed to play a catalytic role in the fast pyrolysis process, and in the absence of a catalyst, the fast quenching of volatile species produces a product stream rich in hydrogen-free sugars; 2) XPS and FT-IR and SEM (fig. 4, 5, 6) analysis showed that the lignin structure around the outside of the cellulose was destroyed, the cellulose was exposed, thereby promoting sugar out-diffusion, and relative enrichment of cellulose after lignin removal resulted in higher LG content in the pyrolysis stream; 3) due to the change of the pore structure on the surface of the biomass after pretreatment, the change of the heat transfer coefficient and the volatile component escape way also change the pyrolysis yield of the carbohydrate.
Also, the increase in relative content of hemicellulose resulted in an increase in furfural content from 4.03% to 14.14%. 2-methoxy radical due to lack of catalysis of ash on lignin pyrolysis and reduction versus lignin contentThe contents of the 4-vinylphenol and the 2, 6-dimethoxyphenol are respectively reduced from 9.03 percent and 6.66 percent to 0 percent (the detection limit is not reached). It is believed that the methyl o-quinone dissociates from other free radicals through hydrogen abstraction, forming intermediates for the 2, 3-benzofuran produced during biomass pyrolysis. The 2.3-benzofuran is then reduced to form the 2.3-dihydrobenzofuran. The reduction of the intermediate free radical leads to a substantial reduction in 2, 3-dihydrobenzofuran. After pretreatment, the aromatics are largely reduced, however, rearrangement reactions during pyrolysis of cellulose result in the presence of a constant amount of phenol in the pyrolysis oil. 5-hydroxymethylfurfural is a product of cellulose depolymerization. Under certain conditions, it can be interconverted with LG. Therefore, an increase in the LG content also leads to an increase in the 5-hydroxymethylfurfural content. With increasing pretreatment time and increasing NaCl concentration, the sugar content rose to 31.25% and 25.04%, respectively. Due to the presence of Na, LG undergoes a ring-opening reaction during pyrolysis and is converted into other substances. Therefore, although the cellulose content after pretreatment with high NaCl concentration is higher than that of the sample of 15V-8h, the LG produced by pyrolysis is less. In addition, the dehydration reaction results in the formation of cellulose anhydro units, which are then converted to LG. However, ClOx -The characteristic chain ends of the cellulose are oxidized. The absence of characteristic chain ends and dehydration units results in a reduction in the relative content of LG.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for promoting the quality of pyrolysis oil by seawater electrochemical pretreatment of biomass is characterized by comprising the following steps:
(1) electrochemical pretreatment: crushing and screening a biomass raw material, adding the crushed and screened biomass raw material into a salt solution, uniformly mixing, then carrying out an electrolytic reaction under the conditions of stirring and applied voltage, wherein the voltage is 5-15V and the time is 2-8 hours, and after the reaction is finished, carrying out suction filtration, washing and drying to obtain a pretreated biomass; wherein the salt solution is a NaCl solution or seawater with the concentration of 2-6.5% by mass;
(2) pyrolysis: and (2) pyrolyzing the pretreated biomass obtained in the step (1) in a protective gas atmosphere at 400-600 ℃ for 30-90 min, and collecting pyrolysis oil by using an organic solvent.
2. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 1, wherein the method comprises the following steps:
the concentration of the NaCl solution in the step (1) is 2-5% by mass;
the solid-liquid ratio of the biomass raw material to the salt solution in the step (1) is 1: 100 to 150 parts; g/ml.
3. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 2, wherein the method comprises the following steps:
the concentration of the NaCl solution in the step (1) is 2-3.5% by mass;
the solid-liquid ratio of the biomass raw material to the salt solution in the step (1) is 1: 100, respectively; g/ml.
4. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 3, wherein the method comprises the following steps:
the concentration of the NaCl solution in the step (1) is 3.5 percent by mass.
5. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 1, wherein the method comprises the following steps:
the stirring conditions in the step (1) are as follows: stirring at 400-800 r/min for 10-40 min;
the voltage of the electrolytic reaction in the step (1) is 10-15V;
the time of the electrolytic reaction in the step (1) is 4-8 hours;
the pyrolysis temperature in the step (2) is 500 ℃;
the pyrolysis time in the step (2) is 30 min;
the condensation temperature during the collection in the step (2) is-10 to-20 ℃;
the organic solvent in the step (2) is acetone.
6. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 5, wherein the method comprises the following steps:
the stirring conditions in the step (1) are as follows: stirring at 600r/min for 20 min;
the voltage of the electrolytic reaction in the step (1) is 15V;
the time of the electrolytic reaction in the step (1) is 8 hours;
the condensation temperature at the time of collection described in step (2) was-18 ℃.
7. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 1, wherein the method comprises the following steps:
the electrode used in the electrochemical pretreatment in the step (1) is a graphite electrode, the distance between the two electrodes is 6cm, the power supply is an adjustable direct current power supply, and the electrolytic cell is a diaphragm-free electrolytic cell;
and (3) collecting in the step (2) in a condensing device, wherein the condensed liquid in the condensing device is industrial ethanol.
8. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 1, wherein the method comprises the following steps:
the biomass raw material in the step (1) is a waste agriculture and forestry biomass raw material;
sieving in the step (1) is to sieve the mixture by a sieve of 40-200 meshes;
the washing in the step (1) is washing by sequentially adopting water, acetone and water;
the drying temperature in the step (1) is 50-105 ℃;
the drying time in the step (1) is 5-24 hours;
the protective gas in the step (2) is inert gas.
9. The method for promoting the upgrading of the pyrolysis oil by electrochemically pretreating the biomass with the seawater according to claim 8, wherein the method comprises the following steps:
the biomass raw material in the step (1) is corn straw;
sieving in the step (1) is to pass through a sieve of 80-100 meshes;
the drying temperature in the step (1) is 105 ℃;
the drying time in the step (1) is 8 hours;
the protective gas in the step (2) is nitrogen, and the gas flow is 400-600 ml/min.
10. Application of the method for promoting quality of pyrolysis oil by electrochemically pretreating biomass with seawater according to any one of claims 1 to 9 in preparation of pyrolysis oil, levoglucosan and/or furfural.
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